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| United States Patent |
5,071,738
|
|
Mizukura
, et al.
|
December 10, 1991
|
Silver halide photographic material
Abstract
The present invention relates to a silver halide photographic material that
has at least one photographic constituent layer on a support, which
photographic material is characterized in that said at least one
photographic constituent layer contains a dispersion obtained by
emulsifying and dispersing at least one hydrophobic, photographically
useful material and at least one polymer compound that is water-insoluble
but soluble in organic solvents and which has a phenolic hydroxyl group.
| Inventors:
|
Mizukura; Noboru (Hino, JP);
Ohashi; Hakubun (Hino, JP);
Sugita; Shuichi (Hino, JP)
|
| Assignee:
|
Konica Corporation (Tokyo, JP)
|
| Appl. No.:
|
480264 |
| Filed:
|
February 15, 1990 |
Foreign Application Priority Data
| Current U.S. Class: |
430/546; 430/627 |
| Intern'l Class: |
G03C 001/38 |
| Field of Search: |
430/546,548,627
|
References Cited
U.S. Patent Documents
| 4362812 | Dec., 1982 | Minamizono et al. | 430/528.
|
| 4656124 | Apr., 1987 | Komamura | 430/548.
|
| 4874689 | Oct., 1989 | Yamanouchi et al. | 430/548.
|
Primary Examiner: Bowers, Jr.; Charles L.
Assistant Examiner: Baxter; Janet C.
Attorney, Agent or Firm: Bierman; Jordan B.
Claims
What is claimed is:
1. A silver halide photographic material developable with color developers
at a temperature of 20.degree. C. to 50.degree. C., said material
comprising at least one photographic layer on a support, said layer
containing a dispersion of at least one hydrophobic, dye image forming
coupler, and at least one polymer compound formed of at least one monomer
selected from the group consisting of
##STR9##
said polymer compound being water-insoluble but soluble in organic
solvents.
2. A silver halide photographic material according to claim 1 wherein said
polymer compound contains a copolymer formed of said monomer and at least
one monomer selected from the group consisting of acrylate, methacrylate,
acrylamide and methacrylamide compounds.
3. A silver halide photographic material according to claim 1 wherein said
polymer compound has a number average molecular weight of no more than
2.times.10.sup.5.
4. A silver halide photographic material according to claim 1 wherein said
polymer compound has a number average molecular weight of from
5.times.10.sup.3 to 1.times.10.sup.5.
5. A silver halide photographic material according to claim 1 wherein the
weight ratio of said polymer compound to said hydrophobic, dye image
forming coupler is within the range of from 1:20 to 20:1.
6. A silver halide photographic material according to claim 1 wherein the
weight ratio of said polymer compound to said hydrophobic, dye image
forming coupler is within the range of from 1:10 to 10:1.
7. A silver halide photographic material according to claim 1 wherein said
dye image forming coupler is at least one member selected from the group
consisting of a benzoyl acetanilide type coupler, a pivaloyl acetanilide
type coupler, a 5-pyrazolone based coupler, a pyrazolotriazole based
coupler, an imidazole based coupler, a pyrazolopyrazole based coupler, a
pyrazolotetrazole based coupler, a pyrazolinobenzimidazole based coupler,
an indazolone based coupler, a phenolic coupler, a naphtholic coupler, and
a pyrazoloquinazolone based coupler.
8. A silver halide photographic material according to claim 1 wherein the
silver halide grains contained in said photographic constituent layer has
a silver chloride content of at least 90 mol%, a silver bromide content of
no more than 10 mol%, and a silver iodide content of no more than 0.5
mol%.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic material,
particularly to a silver halide photographic material that is improved in
color forming ability, storage stability of dye image and film properties.
The most common method of forming dye images with silver halide color
photographic materials is to form dyes by the reaction between
photographic couplers and the oxidation product of color developing
agents. For ordinary color reproduction, magenta, yellow and cyan couplers
are used as photographic couplers, and aromatic primary amino color
developing agents are used as color developing agents to form azomethine
dyes, indoaniline dyes and other dyes. The couplers described above are
usually incorporated in separate light-sensitive layers in superposition.
Besides these light-sensitive layers, non-light-sensitive layers and
protective layers also contain anti-color mixing agents, ultraviolet (uv)
absorbers and other additives with a view to improving the quality of
image and the storage stability of dye image.
Thus, many additives are incorporated in silver halide photographic
materials in order to have silver halides exhibit their characteristics to
the fullest extent. The additives incorporated in silver halide
photographic materials are versatile in water solubility and range from
water-soluble to water-insoluble compounds. Examples of "hydrophobic"
compounds which are insoluble or slightly soluble in water include dye
image forming couplers, ultraviolet absorbers, antifading agents,
anti-color mixing agents, redox compounds and anti-foggants. In order to
incorporate these hydrophobic compounds into hydrophilic colloidal layers,
they must be finely dispersed to form an emulsion of an oil-in-water or
"oil protected" type. While several methods have been proposed to disperse
hydrophobic compounds, one approach is to disperse them in the presence of
surfactants together with organic solvents such as dibutyl phthalate and
tricresyl phosphate, as described in U.S. Pat. Nos. 2,322,027, 2,835,579,
3,748,141, JP-B-54-24288 (the term "JP-B" as used herein means an
"examined Japanese patent publication") and JP-A-56-114940 (the term
"JP-A" as used herein means an "unexamined published Japanese patent
application"), and another approach is to disperse hydrophobic compounds
together with polymer compounds, as described in U.S. Pat. Nos. 2,772,163,
2,852,382 and JP-A-51-25133.
These methods, however, have been found to be unsatisfactory in one way or
another. For instance, they cause deterioration in color forming ability
and lightfastness. Even if these problems can be avoided, dye images, when
stored in a humid condition, will deteriorate in the gloss of film
surface. The deterioration in color forming ability has been particularly
great when developers that do not contain benzyl alcohol are used. As for
the method that disperses hydrophobic compounds together with polymer
compounds, the deterioration of color forming ability can be prevented to
some extent by increasing the proportion of hydrophilic monomers such as
acrylic acid but the improvement is still insufficient to produce
completely satisfactory light-sensitive materials.
JP-A-63-44658 describes an invention that intends to improve the storage
stability of image by dispersing a specific dye image forming coupler
together with a polymer compound in the absence of a high-boiling point
organic solvent. This methods is effective to some extent in improving the
storage stability of image but on the other hand, it causes a substantial
deterioration in color forming ability.
SUMMARY OF THE INVENTION
An object, therefore, of the present invention is to provide a silver
halide photographic material that is high in both color forming ability
and storage stability of image.
Another object of the present invention is to provide a silver halide
photographic material that exhibits satisfactory color forming ability
even if it is processed with a color developer that is substantially free
of benzyl alcohol.
A further object of the present invention is to provide a silver halide
photographic material that has high film strength and that will not
experience any deterioration in the gloss of film surface even if it is
stored in a humid condition.
These objects of the present invention can be attained by a silver halide
photographic material that has at least one photographic constituent layer
on a support, which photographic material is characterized in that said at
least one photographic constituent layer contains a dispersion of at least
one hydrophobic, photographically useful material and at least one polymer
compound that is water-insoluble but soluble in organic solvents and which
has a phenolic hydroxyl group.
DETAILED DESCRIPTION OF THE INVENTION
One important aspect of the present invention is to use a polymer compound
that is water-insoluble but soluble in organic solvents and which has a
phenolic hydroxyl group (this is hereinafter referred to as the "polymer
compound of the present invention".) The pKa of the phenolic hydroxyl
group in the polymer compound of the present invention is not limited to
any particular value but it is preferably within the range of from 6 to
11, with the range of 6.5-10.5 being particularly preferred. A monomer
that is preferably used to form the polymer compound of the present
invention is represented by the following general formula (I):
##STR1##
where R.sub.1 is a hydrogen atom, an alkyl group of 1-4 carbon atoms or a
hydrogen atom; R.sub.2 is a monovalent substituent; X.sub.1 and X.sub.2
are each
##STR2##
provided that R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each
represents a hydrogen atom or an alkyl group; J.sub.1 and J2 are each an
alkylene group, an arylene group or an aralkylene group; l is an integer
of 0-4; m, n, o and p are each an integer of 0 or 1.
Examples of the alkyl group having 1-4 carbon atoms that is represented by
R.sub.1 in the general formula (I) include methyl, ethyl, propyl and butyl
groups, and examples of the halogen atom represented by R.sub.1 include
fluorine, chlorine and bromine atoms. Examples of the monovalent
substituent represented by R.sub.2 include: an alkyl group such as methyl,
ethyl, propyl or t-butyl; a nitro group; a cyano group; an alkoxy group
such as ethoxy; an acyloxy group such as acetoxy; an acylamino group such
as acetylamino; a sulfonamido group such as methanesulfonamido; a
sulfamoyl group such as methylsulfamoyl; a halogen atom such as fluorine,
chlorine or bromine; a carbamoyl group such as methylcarbamoyl; an
alkoxycarbamoyl group such as methoxycarbamoyl; and a sulfonyl group such
as methylsulfonyl. If l is an integer of 2 or more, these substituents may
be the same or different.
The alkyl group represented by R.sub.3 to R.sub.8 is preferably one having
1 to 6 carbon atoms and may be exemplified by methyl, ethyl, propyl,
iso-propyl, sec-butyl, hexyl, etc.
Examples of the alkylene group represented by J.sub.1 and J.sub.2 in the
general formula (I) include methylene, ethylene, butylene and
1-methylethylene, and examples of the arylene group represented by J.sub.1
and J.sub.2 include phenylene and naphthylene. An example of the
aralkylene group represented by J.sub.1 and J.sub.2 is methylenephenylene.
The alkylene, arylene and aralkylene groups may each have a substituent
represented by R.sub.2.
The following are specific but non-limiting examples of the monomers
capable of forming the polymer compounds of the present invention.
##STR3##
The polymer compound of the present invention may be a homopolymer of the
monomer represented by the general formula (I) or it may be a copolymer of
two or more of such monomers. If desired, it may be a copolymer of these
monomers with other monomers. Monomers that are preferably used to form
copolymers with the monomer represented by the general formula (I) include
acrylates, methacrylates, acrylamides and methacrylamides. Specific
examples of the monomers capable of forming copolymers with the monomer
represented by the general formula (I) are described below.
Illustrative acrylate esters include: methyl acrylate, ethyl acrylate,
isopropyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl
acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, 2-chloroethyl acrylate,
4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate,
dimethylaminoethyl acrylate, methoxybenzyl acrylate, cyclohexyl acrylate,
tetrahydrofurfuryl acrylate, phenyl acrylate,
2,2-dimethyl-3-hydroxy-propyl acrylate, 2-methoxyethyl acrylate,
2-ethoyethyl acrylate, 2-i-propoxy acrylate, 2-(2-methoxyethoxy)ethyl
acrylate, .omega.-methoxypolyethylene glycol acrylate (number of added
moles, n=9), and 1-bromo-2-methoxyethyl acrylate.
Illustrative methacrylate esters include: methyl methacrylate, ethyl
methacrylate, propyl methacrylate, butyl methacrylate, isobutyl
methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl
methacrylate, octyl methacrylate, sulfopropyl methacrylate,
N-ethyl-N-phenylaminoethyl methacrylate, dimethylaminophenoxyethyl
methacrylate, furfuryl methacrylate, phenyl methacrylate, cresyl
methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate,
triethyleneglycol monomethacrylate, 2-methoxyethyl methacrylate,
2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-(2-methoxyethoxy)ethyl methacrylate, .omega.-methoxypolyethylene glycol
methacrylate (number of added moles, n=6), etc.
Illustrative vinyl esters include: vinyl acetate, vinyl propionate, vinyl
butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl
methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate,
etc.
Illustrative acrylamides include: acrylamide, ethyl acrylamide, propyl
acrylamide, butyl acrylamide, t-butyl acrylamide, cyclohexyl acrylamide,
benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide,
dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide,
.beta.-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone
acrylamide, etc.
Illustrative methacrylamides include: methacrylamide, methyl
methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl
methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl
methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide,
dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl
methacrylamide, .beta.-cyanoethyl methacrylamide,
N-(2-acetoacetoxyethyl)methacrylamide, etc.
Other copolymerizable monomers include: olefins such as dicyclopentadiene,
ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene
chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc.;
styrenes such as styrene, methylstyrene, trimethylstyrene, ethylstyrene,
chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene,
methyl vinylbenzoate, etc.; crotonic acid esters such as butyl crotonate,
hexyl crotonate, etc.; diesters of itaconic acid such as dimethyl
itaconate, diethyl itaconate, dibutyl itaconate, etc.; diesters of maleic
acid such as diethyl maleate, dimethyl maleate, dibutyl maleate, etc.;
diesters of fumaric acid such as diethyl fumarate, dimethyl fumarate,
dibutyl fumarate, etc.
Other comonomers that can be used are listed below: allyl compounds such as
allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; vinyl
ethers such as methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl
ether, dimethylaminoethyl vinyl ether, etc.; vinyl ketones such as methyl
vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; vinyl
heterocyclic compounds such as vinylpyridine, N-vinylimidazole,
N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; glycidyl
esters such as glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated
nitriles such as acrylonitrile, methacrylonitrile, etc.
The polymer compound of the present invention may contain an acid group
containing monomer to the extent that will not render said polymer
water-soluble. If an acid group containing monomer is to be contained, its
content is preferably not more than 20 wt% of the polymer compound. The
pKa of the acid group containing monomer is preferably not more than 6.
Examples of the acid group containing monomer include: acrylic acid,
methacrylic acid, itaconic acid, maleic acid, a monoalkyl ester of
itaconic acid, a monoalkyl ester of maleic acid, citraconic acid,
styrenesulfonic acid, vinylbenzylsulfonic acid, acryloyloxyalkylsulfonic
acid, methacryloyloxyalkylsulfonic acid, acrylamidealkylsulfonic acid,
methacrylamidealkylsulfonic acid, acryloyloxyalkyl phosphate,
methacryloyloxyalkyl phosphate, etc. These acids may be in the form of
salts of alkali metals (e.g. Na or K) of ammonium ion.
The polymer compound of the present invention can be prepared by solution
polymerization, bulk polymerization, suspension polymerization or emulsion
polymerization. Initiators for use in these polymerization methods may be
water-soluble or oleophilic ones. Exemplary water-soluble polymerization
initiators include: persulfates such as potassium persulfate, ammonium
persulfate and sodium persulfate; water-soluble azo compounds such as
sodium 4,4'-azobis-4-cyanovalerate and
2,2'-azobis(2-aminodipropane)hydrochloride; and hydrogen peroxide.
Exemplary oleophilic polymerization initiators include: oleophilic azo
compounds such as azobisisobutyronitrile,
2,2'-azobis-2,4-dimethylvale-nitrile,
1,1'-azobis(cyclohexanone-1-carbonitrile), dimethyl
2,2'-azobisisobutyrate, and diethyl 2,2'-azobisisobutyrate; benzoyl
peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, and di-t-butyl
peroxide.
The following are specific but non-limiting examples of the polymer
compound of the present invention, provided that the figures in
parentheses denote the weight ratio of comonomers.
A-1) N-(4-hydroxyphenyl)methacrylamide/methyl methacrylate copolymer
(60:40);
A-2) N-(2-hydroxy-5-ethanesulfonylphenyl)acrylamide/methyl acrylate
copolymer (75:25);
A-3) N-(4-hydroxyphenyl)methacrylamide/N-tert-butyl acrylamide copolymer
(50:50);
A-4) N-(4-hydroxyphenyl)methacrylamide/styrene copolymer (72:28);
A-5) N-[4-(4'-hydroxyphenylsulfonyl)phenyl]acrylamide/n-butyl acrylate
copolymer (65:35);
A-6) [4-(4'-hydroxyphenylsulfonyl)phenyloxymethyl]styrene (mixture of m-
and p-forms)/N-tert-butyl acrylamide copolymer (15:85);
A-7) N-(4-hydroxyphenyl)methacrylamide/methyl methacrylate/N-tert-butyl
acrylamide copolymer (30:40:30);
A-8) poly[N-(4-hydroxyphenyl)acrylamide];
A-9) poly(p-hydroxystyrene);
A-10) poly(m-hydroxystyrene);
A-11) N-[4-(4'-hydroxyphenylsulfonyl)phenyl]acrylamide/vinyl acetate
copolymer (55:45);
A-12) p-hydroxystyrene methyl methacrylate copolymer (70:30);
A-13) N-(3-hydroxyphenyl)vinyl sulfonamide/ethyl acrylate/acrylic acid
copolymer (20:75:5);
A-14) poly(vinyl p-hydroxybenzoate);
A-15) N-[4-4'-hydroxyphenylsulfonyl)phenyl]methacrylamide/methyl
methacrylate copolymer (75:25);
A-16) p-hydroxystyrene/N-tert-butyl acrylamide copolymer (60:40);
A-17) m-hydroxystyrene/N-vinylpyrrolidone copolymer (90:10);
A-18) m-hydroxystyrene/acrylonitrile/vinylidene chloride copolymer
(35:25:40);
A-19) p-hydroxystyrene/2-methoxyethyl acrylate copolymer (30:70); and
A-20) vinyl p-hydroxybenzoate/methyl methacrylate copolymer (40:60).
A specific method of synthesizing polymer compound (A-5) of the present
invention is described below.
Synthesis of monomer (17), N-[4-(4 -hydroxyphenylsulfonyl)
phenyl]-acrylamide:
A mixture of 4-(4'-hydroxyphenylsulfonyl)aniline (23.3 g), pyridine (9.4 g)
and nitrobenzene (1 ml) is added to 400 ml of tetrahydrofuran. To the
ice-cooled solution, 9.0 g of acrylic acid chloride is added dropwise and
stirred for 30 min. The stirred mixture is added to 2,000 ml of water and
the precipitating crystal is separated by filtration. The resulting
crystal is recrystallized with ethanol to obtain the end compound in an
amount of 28.5 g. The structure of this compound is verified by IR, NMR
and mass spectra.
Polymerization
A mixture of N-[4-(4'-hydroxyphenylsulfonyl)phenyl] acrylamide (6.5 g),
n-butyl acrylamide (3.5 g) and DMF (100 ml) is stirred in a nitrogen
stream at 80.degree. C. To the stirred mixture, 0.5 g of
dimethyl-2,2'-azobisisobutyrate dissolved in 5 ml of DMF is added and
reaction is performed for 6 h. The reacted DMF solution is added dropwise
to 2,000 ml of water and the precipitating solids are separated by
filtration. After washing with water, the solids are dried to obtain the
end product in an amount of 9.5 g.
The number average molecular weight of the polymer compound of the present
invention is not limited to any particular value but is preferably not
more than 2.times.10.sup.5, more preferably in the range of
5.times.10.sup.3 to 1.times.10.sup.5.
The weight ratio of the polymer compound of the present invention to a
hydrophobic, photographically useful material is preferably within the
range of from 1:20 to 20:1, more preferably in the range of from 1:10 to
10:1.
Examples of the hydrophobic, photographically useful material that may be
used in the present invention include dye image forming couplers, uv
absorbers, anti-fading agents, anti-color mixing agents, redox compounds,
anti-foggants, etc.
Dye image forming couplers that are used with particular preference in the
present invention are described below. Illustrative yellow dye image
forming couplers include benzoyl acetanilide and pivaloyl acetanilide type
couplers. Illustrative magenta dye image forming couplers include
5-pyrazolone, pyrazolotriazole, imidazopyrazole, pyrazolopyrazole,
pyrazolotetrazole, pyrazolinobenzimidazole, and indazolone based couplers.
Illustrative cyan dye image forming couplers include phenolic, naphtholic
and pyrazoloquinazolone based couplers. Specific examples of these yellow,
magenta and cyan dye forming couplers are known in the photographic
industry and all of the known dye image forming couplers are included
within the scope of the present invention.
Typical examples of yellow dye image forming couplers that can be used in
the present invention are listed below.
##STR4##
These yellow dye image forming couplers embrace the compounds described in,
for example, German Patent Application (OLS) Nos. 2,057,941, 2,163,812,
1,491,616, U.S. Pat. Nos. 4,404,234, 3,730,722, 4,057,452, 4,133,958,
4,022,620, 4,314,023, 4,314,023, 4,008,086, 4,008,086 and 4,314,023, and
they can be synthesized by the methods described in the patents.
Typical examples of magenta dye image forming couplers that can be used in
the present invention are listed below.
##STR5##
These magenta dye image forming couplers embrace the compounds described
in, for example, U.S. Pat. No. 3,684,514, British Patent No. 1,183,515,
U.S. Pat. No. 3,725,067, British Patent Nos. 1,252,418 and 1,334,515, and
Research Disclosure No. 24626 (1984), and they can be synthesized by the
methods described in these documents.
The cyan dye image forming couplers that can be used in the present
invention are in no way limited but they are preferably phenolic cyan dye
image forming couplers. The following are typical examples of cyan dye
image forming couplers.
##STR6##
These cyan dye image forming couplers embrace the compounds described in,
for example, U.S. Pat. Nos. 2,423,730 and 2,801,171, and they can be
synthesized by the methods described in these patents.
The dispersion of the hydrophobic, photographically useful material and the
polymer compound of the present invention may be prepared by the following
procedure First, they are dissolved in a low-boiling point organic solvent
and/or a water-soluble organic solvent as required, and emulsified and
dispersed in a hydrophilic binder such as an aqueous gelatin solution in
the presence of a surfactant by suitable dispersing means such as a
stirrer, a homogenizer, a colloid mill, a flow-jet mixer or an ultrasonic
apparatus. The thus prepared dispersion is added to a hydrophilic
colloidal layer of interest. The low-boiling point organic solvent and/or
water-soluble organic solvent may be removed from the resulting dispersion
by some suitable method such as evaporation, noodle washing or
ultrafiltration.
Illustrative low-boiling point organic solvents include ethyl acetate,
butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone,
methyl isobutyl ketone, .beta.-ethoxyethyl acetate, methyl cellosolve
acetate and cyclohexanone. Illustrative water-soluble organic solvents
include methyl alcohol, ethyl alcohol, acetone and tetrahydrofuran. These
organic solvents may be used either independently or in combination with
themselves as required. Another method of preparing the dispersion of the
hydrophobic, photographically useful material and the polymer compound of
the present invention is described in JP-A-60-107642. According to this
method, the monomer component or components of the polymer compound of the
present invention are subjected to suspension polymerization, solution
polymerization or bulk polymerization in the presence of the hydrophobic,
photographically useful material and the resulting polymer is emulsified
and dispersed in a hydrophilic binder by the method already described
above.
The further method of preparing the dispersion of the hydrophobic,
photographically useful material and the polymer compound of the present
invention is described in U.S. Pat. No. 4,199,363, JP-A-58-17,152,
JP-A-60-18,541, JP-A-62-96,941 and JP-A-63-43,903. According to this
method, the polymer compounds are emulsified and dispersed and then the
resulting dispersion is loaded with the hydrophobic, photographically
useful material.
The thus prepared dispersion of the hydrophobic, photographically useful
material and the polymer compound of the present invention may contain a
high-boiling point organic solvent selected from among those organic
solvents which have boiling points not lower than 150.degree. C and that
will not react with the oxidation product of developing agents, such as
phenolic derivatives, phthalate esters, phosphate esters, citrate ester,
benzoate ester, alkylamides, aliphatic acid esters and trimesic acid
esters.
The dispersion described above is preferably incorporated in silver halide
emulsion layers. Any silver halide can be used in the present invention,
as illustrated by silver chloride, silver bromide, silver iodide, silver
chlorobromide, silver iodobromide, and silver chloroiodide. If rapid
processing is required as in the case of processing color paper, silver
halide grains having a silver chloride content of at least 90 mol % are
preferably used, with the silver bromide and silver iodide contents being
preferably not more than 10 mol % and 0.5 mol %, respectively. Silver
chloro-bromide grains with a silver bromide content of 0.1-2 mol % are
more preferred. Such silver halide grains may be used either independently
or in admixture with other silver halide grains having different
compositions. If desired, they may be used in admixture with silver halide
grains having a silver chloride content of not more than 90 mol %. If
silver halide grains having a silver chloride content of more than 90 mol
% are to be incorporated in a silver halide emulsion layer, those silver
halide grains generally occupy at least 60 wt %, preferably at least 80 wt
%, of the total silver halide grains in said emulsion layer.
Gelatin is advantageously used as a binder in the present invention but
other hydrophilic colloids may also be used, as illustrated by gelatin
derivatives, graft polymers of gelatin and other high-molecular weight
compounds, proteins other than those mentioned above, sugar derivatives,
cellulose derivatives, and synthetic hydrophilic high-molecular weight
materials such as homo- and copolymers.
Dye image forming couplers to be used in the silver halide photographic
material of the present invention are commonly selected in such a way that
dyes that absorb light to which the emulsion layers have spectral
sensitivity will be formed in the respective emulsion layers. Thus, a
yellow dye image forming coupler is used in a blue-sensitive emulsion
layer, a magenta dye image forming coupler in a green-sensitive emulsion
layer, and a cyan dye image forming coupler in a red-sensitive emulsion
layer. However, depending on the object, other combinations of couplers
may be employed to form a specific silver halide color photographic
material.
To form image, the photographic material of the present invention may be
subjected to any of the color development processes known in the art. The
color developing agent to be used in color developers in accordance with
the present invention may be selected from known compounds that are used
extensively in various color photographic processes. Suitable developing
agents include aminophenolic and p-phenylenediamino derivatives. These
compounds are used in the form of salts, such as hydrochlorides or
sulfates, which are stabler than when those compounds are in the free
state. These compounds are used at concentrations that generally range
from about 0.1 g to about 30 g, more preferably from about 1 g to about 15
g, per liter of color developer.
Illustrative aminophenolic developers include o-aminophenol, p-aminophenol,
5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene,
2-hydroxy-3-amino-1,4-dimethylbenzene. Particularly useful primary
aromatic amino color developing agents are N,N-dialkyl-p-phenylenediamino
compounds, in which the alkyl and phenyl groups may have any suitable
substitutents. Particularly useful compounds may be exemplified by, for
example, N,N-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine
hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene,
N-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-.beta.-hydroxyethylaminoaniline,
4-amino-3-methyl-N,N-diethylaniline, and
4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.
Besides these primary aromatic amino color developing agents, compounds
that are known components of developers may be added to the color
developer for use in processing the silver halide photographic material of
the present invention, and they include alkali agents such as sodium
hydroxide, sodium carbonate and potassium carbonate, as well as alkali
metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali
metal halides, benzyl alcohol, water softeners and thickening agents.
The pH of the color developer is generally at least 7, most commonly in the
range of from about 10 to 13. Color development is usually performed at a
temperature of at least 15.degree. C., more commonly in the range of
20.degree.-50.degree. C. For rapid development, temperatures of at least
30.degree. C. are preferred.
The silver halide photographic material of the present invention is
preferably processed with a color developer that is free from benzyl
alcohol.
After color development, the silver halide photographic material of the
present invention is subjected to bleaching and fixing treatments.
Bleaching may be performed simultaneously with fixing. While many
compounds are usable as bleaching agents, compounds of polyvalent metals
such as iron (III), cobalt (III) and copper (II) are typical. In
particular, complex salts of these polyvalent metal cations and organic
acids such as aminopolycarboxylic acids (e.g. ethylenediaminetetraacetic
acid, nitrilotriacetic acid and N-hydroxyethylethylenediaminediacetic
acid), malonic acid, tartaric acid, malic acid, diglycolic acid and
dithioglycolic acid, or ferricyanates and bichromates may be used either
independently or in appropriate combinations.
Soluble complexing agents that solubilize silver halides as complex salts
may be used as fixing agents. Examples of such soluble complexing agents
include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate,
thiourea and thioether.
After fixing, the photographic material is usually washed with water.
Washing with water may be replaced by a stabilizing treatment. If desired,
both washing and stabilizing treatments may be performed.
The following examples for the purpose of further illustrating the present
invention but are in no way to be taken as limiting.
EXAMPLE 1
A paper base laminated with polyethylene on one side and with TiO.sub.2
containing polyethylene on the other side in contact with the first layer
was coated with layers in accordance with the arrangement shown in Table
1, to thereby fabricate a multi-layered silver halide color photographic
material (sample No. 101). The necessary coating solutions were prepared
in the following manner.
Preparation of a dispersion of cyan dye image forming coupler
Twelve grams of a cyan dye image forming coupler (C-2), 10 g of a
high-boiling point organic solvent (DBP) and 18 g of polymer compound
(A-5) of the present invention having an average molecular weight of ca.
2.times.10.sup.4 were dissolved in 40 ml of ethyl acetate. Using a
homogenizer, the resulting solution was emulsified and dispersed in 200 ml
of a 10% aqueous gelatin solution containing 10 ml of a solution of 10%
sodium alkylnaphthalenesulfonate, to thereby form a dispersion of the cyan
dye image forming coupler.
The resulting dispersion was mixed with a red-sensitive silver
chlorobromide emulsion (30 mol % AgCl; 70 mol% AgBr; 10 g in terms of
silver) and a coating gelatin solution to prepare a coating solution for
the fifth layer. Coating solutions for the other layers were similarly
prepared as shown in Tables 1 and 2.
As a gelatin hardener, compound H-1 (see below) was added in an amount of
0.08 g/m.sup.2.
##STR7##
TABLE 1
______________________________________
Amount,
Layer Composition g/m.sup.2
______________________________________
7th layer Gelatin 1.0
(protective
layer)
6th layer Gelatin 0.6
(uv absorbing
uv absorber (UV-1) 0.2
layer) uv absorber (UV-2) 0.2
Anti-color mixing agent (HQ-1)
0.01
DBP 0.2
5th layer Gelatin 1.40
(red-sensitive
Red-sensitive AgClBr emulsion
0.24
layer) (30% AgCl, 70% AgBr), as Ag
Cyan dye image forming coupler
0.7*
(see Table 2)
Polymer compound of the
0.53
present invention
(see Table 2)
DBP 0.30
4th layer Gelatin 1.30
(uv absorbing
uv absorber (UV-1) 0.40
layer) uv absorber (UV-2) 0.40
Anti-color mixing agent (HQ-1)
0.03
DBP 0.40
3rd layer Gelatin 1.40
(green- Green-sensitive AgClBr emulsion
0.21
sensitive (30% AgCl, 70% AgBr), as Ag
layer) magenta dye image forming coupler
0.7*
(see Table 2)
Dye image stabilizer (ST-1)
0.20
Dye image stabilizer (ST-2)
0.10
Anti-stain agent (HQ-1)
0.01
Polymer compound of the
0.60
present invention
(see Table 2)
DBP 0.30
2nd layer Gelatin 1.20
(intermediate
Anti-color mixing agent (HQ-1)
0.12
layer) DBP 0.15
1st layer Gelatin 1.30
(blue- Blue-sensitive AgClBr emulsion
0.30
sensitive (10% AgCl, 90% AgBr), as Ag
layer) Yellow dye image forming coupler
1.0*
(see Table 2)
Anti-stain agent (HQ-1)
0.02
Polymer compound of the
0.82
present invention
(see Table 2)
DBP 0.40
Base Polyethylene-laminated paper
______________________________________
*millimole/m.sup.2
##STR8##
Additional samples (Nos. 102-110) were fabricated by repeating the same
procedure as described above except that the type of dye image forming
couplers in the first, third and fifth layers, the type of polymer
compound of the present invention and the amount of DBP were changed as
shown in Table 2.
The samples thus fabricated were exposed through an optical wedge in a
sensitometer Model KS-7 (Konica Corp.) and subsequently processed in
accordance with the scheme shown below.
______________________________________
Processing steps
Time Temperature, .degree.C.
______________________________________
Color development
3 min and 30 sec
33
Bleach-fixing
1 min and 30 sec
33
Washing 3 min 33
______________________________________
Formula of color developer
N-Ethyl-N-.beta.-methanesulfonamidoethyl-
4.9 g
3-methyl-4-aminoaniline sulfate
Hydroxylamine sulfate 2.0 g
Potassium carbonate 25.0 g
Sodium bromide 0.6 g
Anhydrous sodium sulfite
2.0 g
Benzyl alcohol 13 ml
Polyethylene glycol (average degree of
3.0 ml
polymerization, 400)
Water to make 1,000
ml
pH adjusted to 10.0 with sodium hydroxide.
Formula of bleach-fixing solution
Ethylenediaminetetraacetic acid iron (III)
sodium salt 6.0 g
Ammonium thiosulfate 100 g
Sodium bisulfite 10 g
Sodium metabisulfite 3 g
Water to make 1,000
ml
pH adjusted to 7.0 with aqueous ammonia.
______________________________________
The processed samples were subjected to the following measurements.
Color forming ability
Maximum color reflection density measurements were conducted with an
optical densitometer (Model PDA-65 of Konica Corp.).
Deterioration of surface gloss
The samples were stored for 7 days at 85.degree. C. and at a relative
humidity of 60%. The surface gloss (%) of each sample was measured with a
glossmeter (Tokyo Denshoku Co., Ltd.) at an incident angle of 60.degree..
The results of the measurements are shown in Table 2.
TABLE 2
__________________________________________________________________________
Fifth
First layer Third layer layer
Sample
Yellow
Polymer
DBP
Magenta
Polymer
DBP
Cyan
No. coupler
compound
g/m.sup.2
coupler
compound
g/m.sup.2
coupler
__________________________________________________________________________
101 Y-2 A-5 0.40
M-8 A-5 0.30
C-2
102 Y-2 A-5 0.20
M-8 A-5 0.10
C-2
103 Y-2 A-3 0.20
M-8 A-3 0.10
C-2
104 Y-2 A-6 0.20
M-8 A-6 0.10
C-2
105 Y-7 A-6 0.20
M-4 A-6 0.10
C-2
106 Y-7 A-6 -- M-4 A-6 -- C-2
107 Y-2 A-5 0.15
M-17
A-3 0.12
C-2
108 Y-2 Comparative
0.40
M-17
Comparative
0.30
C-2
polymer polymer
compound 1 compound 1
109 Y-2 Comparative
-- M-17
Comparative
-- C-2
polymer polymer
compound 1 compound 1
110 Y-7 Comparative
-- M-4 Comparative
-- C-2
polymer polymer
compound 2 compound 2
__________________________________________________________________________
Surface
gloss
Fifth layer after
Sample
Polymer
DBP
Maximum color density
storage
No. compound
g/m.sup.2
Yellow
Magenta
Cyan
(%) Remarks
__________________________________________________________________________
101 A-5 0.30
2.22
2.63 2.48
89 The present
102 A-5 0.10
2.18
2.55 2.35
91 invention
103 A-3 0.10
2.20
2.53 2.41
90
104 A-6 0.10
2.16
2.49 2.36
92
105 A-6 0.10
2.21
2.57 2.39
91
106 A-6 -- 2.13
2.40 2.33
93
107 A-6 0.08
2.19
2.51 2.40
91
108 Comparative
0.30
2.02
2.25 2.30
83 Com-
polymer parision
compound 1
109 Comparative
-- 1.72
1.83 1.66
90
polymer
compound 1
110 Comparative
-- 1.88
2.10 1.55
89
polymer
compound 2
__________________________________________________________________________
As is clear from Table 2, sample Nos. 101-107 using polymer compounds
within the scope of the present invention were satisfactory since they
produced high values of maximum color density for yellow, magenta and cyan
colors and at the same time, their surface gloss did not deteriorate
greatly during storage. Further, these samples had good color forming
ability since they did not experience a substantial decrease in maximum
color density even when the high-boiling point organic solvent (DBP) was
used in a decreasing amount. On the other hand, sample No. 108 which did
not use a compound within the scope of the present invention experienced
substantial deterioration in surface gloss during storage although it was
fairly satisfactory in terms of maximum color density. Other comparative
samples (Nos. 109 and 110) which also did not use a compound within the
scope of the present invention retained comparatively satisfactory surface
gloss after storage but on the other hand, they experienced a substantial
decrease in maximum color density.
EXAMPLE 2
Additional samples of multi-layered silver halide color photographic
material (Nos. 201-210) were fabricated as in Example 1 except that the
compositions of the blue-sensitive AgClBr emulsion in the first layer, the
green-sensitive AgClBr emulsion in the third layer and the red-sensitive
AgClBr emulsion in the fifth layer were changed to one consisting of 99.5
mol % AgCl and 0.5 mol % AgBr. The type of dye image forming couplers in
the first, third and fifth layers, the type of polymer compounds of the
present invention and the amount of DBP were the same as shown in Table 2.
The samples thus fabricated were exposed through an optical wedge as in
Example 1 and subsequently processed in accordance with the following
scheme.
______________________________________
Processing steps
Temperature, .degree.C.
Time, sec
______________________________________
Color development
35.0 .+-. 0.3
45
Bleach-fixing 35.0 .+-. 0.5
45
Stabilizing 30-34 90
Drying 60-80 60
______________________________________
Color developer
Pure water 800 ml
Triethanolamine 10 g
N,N-Diethylhydroxylamine
5 g
Potassium bromide 0.02 g
Potassium chloride 2 g
Potassium sulfite 0.3 g
1-Hydroxyethylidene-1,1-diphosphonic acid
1.0 g
Ethylenediaminetetraacetic acid
1.0 g
Catechol-3,5-disulfonic acid disodium salt
1.0 g
N-Ethyl-N-.beta.-methanesulfonamidoethyl-3-
4.5 g
methyl-4-aminoaniline sulfate
Brightener (4,4'-diaminostilbenedisulfonic
1.0 g
acid derivative)
Potassium carbonate 27 g
Water to make 1,000
ml
pH adjusted to 10.10
Bleach-fixing solution
Ethylenediaminetetraacetic acid iron (III)
Ammonium dihydrate 60 g
Ethylenediaminetetraacetic acid
3 g
Ammonium thiosulfate (70% aq. sol.)
100 ml
Ammonium sulfite (40% aq. sol.)
27.5 ml
Water to make 1,000
ml
pH adjusted to 6.2 with
potassium carbonate or glacial
acetic acid.
Stabilizing solution
5-Chloro-2-methyl-4-isothiazolin-3-one
1.0 g
Ethylene glycol 1.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid
2.0 g
Ethylenediaminetetraacetic acid
1.0 g
Ammonium hydroxide (20% aq. sol.)
3.0 g
Ammonium sulfite 3.0 g
Brightener (4,4' -diaminostilbenedisulfonic
1.5 g
acid derivative)
Water to make 1,000
ml
pH adjusted to 7.0
with sulfuric acid or potassium
hydroxide.
______________________________________
The processed samples were stored for 20 days at 85.degree. C. and 60% r.h.
and their resistance to dark browning was evaluated by measuring the
residual percentage of dye image which initially had a density of 1.0. The
results are shown in Table 3 below.
TABLE 3
______________________________________
Type of couplers and
Maxi-
polymer compounds in
mum Residual
Sample
1st, 3rd, and 5th layers
cyan density
No. and the amount of DBP
density (%) Remarks
______________________________________
201 Same as in sample No. 101
2.38 82 The present
202 Same as in sample No. 102
2.25 81 invention
203 Same as in sample No. 103
2.30 80
204 Same as in sample No. 104
2.31 81
205 Same as in sample No. 105
2.28 83
206 Same as in sample No. 106
2.27 85
207 Same as in sample No. 107
2.32 84
208 Same as in sample No. 108
1.95 72 Comparison
209 Same as in sample No. 109
1.53 75
210 Same as in sample No. 210
1.48 73
______________________________________
As is clear from Table 3, sample Nos. 201-207 which used polymer compounds
within the scope of the present invention produced a satisfactorily high
maximum color density even when they were processed with a color developer
containing no benzyl alcohol. Further the image they produced was
satisfactorily resistant to dark browning. On the other hand, comparative
samples (Nos. 208-210) were poor in both maximum color density and
resistance to dark browning. Measurements were also conducted to evaluate
the capability of forming yellow and magenta colors. Samples Nos. 201-207
using the polymer compounds within the scope of the present invention were
satisfactory informing both yellow and magenta colors at high density. In
addition, the images produced had good keeping quality.
EXAMPLE 3
Additional samples were fabricated as in Example 1 except that DBP in the
6th layer is changed to a polymer compound (A-3), (A-6) or (A-13) of the
present invention.
The samples thus fabricated were exposed through an optical wedge and
subsequently processed us in Example 1.
The processed samples were satisfactory since their surface gloss did not
deteriorate greatly during storage.
As will be understood from the foregoing description, the present invention
provides a silver halide photographic material that is improved not only
in color forming ability and surface gloss after storage but also in the
keeping quality of image.
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